Process for the production of metal soaps of epoxydized fatty acids



A. szczl-:PANEK ETAL 3,459,776

PROCESS FOR THE PRODUCTION OF METAL SOAPS 0F EPOXYDIZED FATTY ACIDS Filed April 1. 1964 EP Q2 INVENTORS ALFRED SZCZEPANEK MARGARETE SZCZEPANEK www i 3,459,776 PROCESS FOR THE PRGDUCTN F METAL SGAPS @F EPOXYDLIZED FATTY ACIDS Alfred Szczepaneir and Margarete Szczepanek, Buren,

Germany, assignors, by mesne assignments to Hoesch- Chemie Geselischaft mit beschrankter Haftung Duren- Chemie, Duran, Rhineland, Germany, a corporation of Germany `Coutiuuation-in-part of application Ser. No. 114,293, .lune Z, 1961. This application Apr. l, 1964, Ser. No. 356,473 Claims priority, application Germany, .lune 3, 1960,

lint.. Cl. (107i 7/24, 5/06, 3/00 U.S. Cl. 260-348 8 Claims The present invention is concerned with the process for the production of metal soaps of epoxidized fatty acids.

This application is a continuation-impart of application Ser. No. 114,293, iiled June 2, 196i, now abandoned.

Metal soaps of epoxidized fatty acids have frequently been proposed for the heat and light stabilizing of halogen-containing synthetic resins.

It is known that metal soaps of saturated and unsaturated fatty acids can be produced by the following processess;

(a) Double reaction between a water-solution alkali metal or ammonium soap of the fatty acids and a watersoluble metal salt;

(b) Reaction of fatty acids with metal oxides, hydroxides, and salts of volatile acids in the melt.

These known processes cannot be used for the production of metal soaps of epoxidized fatty acids without the use of special measures. The epoxy ring is very labile with regard to water, aqueous alkalis and acids, especially at elevated temperatures, whereby glycols or glycol derivatives are formed. Furthermore, epoxy compounds in the presence of certain metal salts have a tendency to polymerize.

In British patent specification No. 754,854, there is described a process for producing metal soaps of epoxidized fatty acids by the neutralization of epoxy fatty acids with alkali at room temperature in an aqueous medium and subsequent precipitation with water-soluble metal salts using the process described above under (a). However, in repeating the process under the described conditions, we found that the products so obtained are not homogeneous and contain considerable amounts of starting material and intermediate products which impairs the usefulness of the epoxy metal soaps.

The saponication of the epoxy fatty acids which are not liquid at room temperature, for example, epoxy stearic acid, with sodium hydroxide in an aqueous medium is incomplete, even with vigorous dispersion and long reaction time, so that the end products are contaminated, after the precipitation, with large amounts of epoxy fatty acid. Furthermore, large amounts of alkali metal soaps are entrained during the precipitation which can only be removed from the reaction product with great diiiiculty.

The epoxy fatty acids, which are liquid or semi-liquid at room temperature, for example, diepoxy-stearic acid, can admittedly be easily saponied at room temperature in an aqueous medium with alkalis in the same manner as their starting substance, linoleic acid, but, nevertheless, the epoxy metal soaps obtained after the precipitation are considerably contaminated with the alkali metal soaps. Corresponding to the unreacted free epoxy fatty acid, there results from the amount of alkali metal hydroxide equivalent hereto by the precipitation with the metal salts, metal hydroxides which, as a result of the their insolubility cannot subsequently be removed by washing and lead to a clouding of the transparent polyvinyl chloride.

3,459,776 Patented Aug. 5, 1969 In the case of some fields of application, alkali metal soaps have an undesired effect by increasing the take up of water, together with an increase of the conductivity and cloudiness.

A further teaching in the prior art is contained in British Patent 825,691. This patent teaches a procedure for making divalent soaps of epoxidized fatty acids, the procedure involving starting with an ester, in particular the epoxidized glyceride or oil, contacting the ester alkali metal hydroxide in an ethanol medium containing a small proportion of Water, namely about 1020% water. This process has the disadvantage of involving destruction of the epoxy groups to an objectionable extent. Further, it has the limitation that the ester of the epoxy fatty acid must be used as starting material.

The object of the present invention is a process of good reproducibility, in which, while preserving the epoxy group, the production of metal soaps of epoxy fatty acids is possible, said soaps being substantially free from start ing materials and intermediate products. According to the present invention, the metal soaps of epoxydized fatty acids are obtained by the double reaction of their alkali metal or ammonium salts with-soluble metal salts. An important factor for the preservation of the epoxy group is the maintenance of a low reaction temperature and a short saponication time for the conversion of the epoxy fatty acids or their esters into the alkali metal or ammonium soaps.

The process takes place in two steps. For example, in the first step, alkali metal soaps are produced by the reaction of epoxidized fatty acids or their esters or glycerides with an aqueous alcoholic solution of alkali metal hydroxides, the alkali metal soaps thus produced then being reacted in a second step with a water-soluble metal salt. In the case of epoxy-stearic acid and magnesium chloride, the reaction takes place according to the following equation:

In the case of the known production of metal soaps, the saponiiication of fatty acids with alkali metal hydroxides, is, in general, carried out at a temperature above the melting point of the acid and in a concentration which is determined by the solubility of the alkali metal soap. in this case, one uses temperatures which are as high as possible and which are dependent upon the melting point of the metal soaps produced, in order to limit the amount of water necessary and in order to increase the throughput rate per reaction vessel. These reaction conditions cannot be applied to the production of alkali metal soaps of epoxy fatty acids since the epoxy group is split olf in an alkali medium at an elevated temperature. Therefore, the reaction with alkali metal hydroxides according to the present invention is preferably carried out at room temperature. As reaction media there are used organic solvents miscible with water, in the form of solutions thereof with water. The preferred organic solvents are alcohols.

With respect to production of the salts, starting with the fatty acids, the invention comprises contacting epoxidized fatty acid in an aqueous, organic liquid, alkaline medium with a monovalent cation for saponiiication to form salt of the epoxidized fatty acid and the cation, and thereafter contacting the salt with an aqueous solution of a water-soluble salt of the polyvalent metal to be produced, to thereby form the polyvalent metal soap product.

With respect to production of the metal soaps starting with the fatty acids or fatty acid esters, and particularly with respect to the use of fatty acid esters as starting material, an aqueous, organic liquid medium for the rst step wherein the saponification is performed, is preferred.

With -respect to the use of aqueous, organic liquid means in the rst step, it has been found, suprisingly, that in effectiveness of the process having particular regard for production with little destruction epoxy groups, the proportion of organic liquid to water is important. The importance of the concentration of the organic liquid is illustrated by the accompanying graphs, wherein:

FIG. l is a graph of time in hours versus the percentage of epoxy groups in the product, with the percent organic liquid as parameter, the organic liquid being ethanol; and

FIG. 2 is a graph of time versus acid number with a parameter as is the case in FIG. l, and also for ethanol as the organic liquid.

The graph of FIG. l shows the decrease of the epoxyoxygen in dependence on time, with the alcoholic content of the solution used as parameter. Decrease in oxygen of the epoxy group is light in alcoholic solutions of up to about 50% (that is, is slight for the curves for 10%, 30% and 50%), but rises sharply in the case of 70% alcohol and more concentrated alcoholic solutions in the desired operating times of 2-4 hours.

The graph of FIG. 2 shows the increase in acid number in dependence on time, the strength of the aqueous alcoholic solutions being again `shown as parameter. A high acid number shows that the saponitication proceeds rapidly in the desired time. For the desired rapid reaction, an alcoholic concentration of at least about 50% is preferred.

The dependence of the variables involved, as is indicated in FIG. l, is generally true for the process of the invention for the acid `and esters as starting materials. FIG. 2 shows dependence of the variables when the starting material is the ester. Thus, the invention provides a procedure permitting the production of the epoxy metal soaps with little destruction of the epoxy groups by suitable `selection of the reaction conditions, particularly the concentration of the organic liquid in the medium employed.

In the figures and throughout the specification and claims, unless otherwise indicated, the concentration of organic liquid is percent of organic liquid based on the organic liquid and water.

The organic solvents used must be at least partially water-soluble and possess a good dissolving power not only for the epoxidized compounds serving as starting materials but also for their alkali metal soaps. The most suitable solvents are the aliphatic Cl-C., branched and straight chain alcohols. Ethanol is preferred. The ratio waterzalcohol is dependent not only upon the nature of the alcohol, but also of the reaction components.

Broadly, the organic liquid content of the medium for the rst step can -be about -70% organic liquid, for example 10-70% alcohol.

With respect to the use of ester, and also the use of acid, as starting material, in general, at low temperature a high content of organic liquid can be used, and as the temperature is increased, the content of alcohol or other organic should be decreased. Thus, at room temperature, an organic liquid content, for example an alcohol content, and in particular an ethanol content, of 50-70% is preferred, whereas at 50 the said content is preferably -50%. If high organic liquid content is used `at high temperature, the destruction of epoxy groups becomes faster than the saponication. Thus, the organic liquid content of the medium is an important factor in realization of suitable saponication rates and suitable retention of epoxy groups. In some cases, production of the product desired will not be realized in the absence of the selection of appropriate organic liquid concentration-temperature relationship.

As a general rule, for selection of a suitable organic liquid concentration-temperature relationship, the reaction temperature for the saponication can be between room temperature and about 60 C., the alcohol content of the medium should correspond to the saponification temperature to provide retention of epoxy groups at least equal to that obtained for the saponication at a temperature of 50 C. and an alcohol content of 30%.

The saponification of the epoxy fatty acid ester is an equilibrium reaction, depending upon temperature and time, in which the saponication and ring opening of the epoxy group proceed simultaneously.

At room temperature and in aqueous alcoholic medium the saponication velocity of the ester is considerably higher than the ring opening velocity of the epoxy group. For the obtaining of metal soaps with a high epoxy oxygen content is is, therefore, important to maintain a suitable reaction time at which the saponiication is as complete as possible and in which the epoxy ring opening is substantially suppressed. The reaction time is dependent upon the nature of the ester and the ratio or water to alcohol. For methyl esters, the saponiiication time amounts to about 0.5 hour and for esters of polybasic alcohols to 2 to 4 hours. In general reaction time is about 0.5-4 hours. The ratio of water to alcohol is, as already mentioned, dependent upon the nature of the ester, of the alcohol and of the solubility of the alkali metal soap formed in the saponication mixture. Furthermore, in the case of certain metal soaps, the degree of polymerization is also influenced.

The dependence of the polymerization of the metal soaps upon the ratio of alcohol to water is particularly noticeable in the case of the saponification of the zinc soaps from epoxidized linseed fatty acid. These soaps can be produced in aqueous alcoholic solution with an ethanol content of more than 50% without difficulty but, in the case of an alcohol content below 50%, products are obtained which, in the case of the epoxy oxygen determination, can no longer be decomposed with hydrochloric acid ether.

Because of the econo-mics of the process, it is advisable to work with the smallest possible amount of alcohol. In general, the alcohol or other organic liquid content of the aqueous solution amounts to l0-70%, preferably 50- 70%, or better 50-60%, and is so chosen that the alkali metal soaps formed are clearly soluble. In the case of acids as starting material, a good range or organic liquid, eg. alcohol, concentration is about 10-60%. The lowest limit of the alcohol content of the saponication mixture amounts to 10% in the case of the epoxidation products of poly-unsaturated acids. Since the saponication does not proceed to completion, the metal soaps of epoxy fatty acids produced according to this process contain small amounts of starting esters which, according to the intended use, are either washed out with organic solvents or, for example, for use as polyvinyl chloride stabilizers, are not disturbing since the epoxydized esters of fatty acids are valuable plasticizers.

The alkaline material used to provide the desired alkaline conditions can be any suitable alkaline material. Instead of alkali metal hydroxides, one can also use alkali metal oxides, metallic oxides or hydroxides which form soluble epoxy metal soaps in the reaction mixture, or ammonium hydroxide or its derivatives. In the case of acids as starting material the alkali metal alcoholates can be used. For the saponication, it is preferred to use the oxides, hydroxides and alcoholates, of Group I of the Periodic System, ammonium hydroxides and its derivatives. In principal, it is also possible to use other basically reacting metal compounds when the metal soaps formed are soluble in the water-alcohol mixture, Potassium and sodium hydroxide are preferred by reason of more rapid reaction.

Esters with monoor polybasic alcohols can be converted in the saponitication to metal soaps. The esters can be produced by the trans-esterilication of unsaturated nat- -urally occurring oils and, if desired, purified by fractional distillation. Glycerides, glycol derivatives, etc. can be ernployed. Where the ester is an ester of a monobasic alcohol, the alcohol can be a lower alkanol having about l- 4 carbon atoms. The alcohol, however, can be a higher alcohol. In general, the aliphatic alcohols can provide the alcohol moiety of the ester.

The epoxy values of epoxydized fatty acids, in contradistinction to their esters, decreases very rapidly upon storage, presumably because the presence of the carboxylic acid group opens the epoxy ring. The technical application of epoxydized fatty acids is thereby rendered diiiicult.

The use of esters renders possible the production of metallic soaps of epoXy-ricinolic acid while avoiding the technically diflicult isolation and puriiicaton of the ricinolic acid.

The rapid saponication of epoxydized esters by aqueous alcoholic alkalis at room temperature is surprising and Was not to be expected since the non-epoxydized esters under these reaction conditions are not or only very slightly saponiliable. The introduction of an epoxy group into a fatty acid ester considerably increases its saponiication velocity.

Epoxydized fatty acids and their esters as starting materials in the sense of the present invention are the prod- The usually powdery products are filtered olf, freed from the alkali metal salts formed during the reaction by washing with water and carefully dried at temperatures of -60 C.

As metal components there are suitable all metals which form metallic soaps with fatty acids. The metal can be a metal of Group II-IV, particularly the following metals: sodium, lithium, magnesium, aluminum lead, calcium, barium, cadmium, zinc and manganese.

For the characterization of the metal soaps the metal content, epoxy oxygen value, melting point and f-ree fatty acid were determined. For the determination of the characterizing data, generally known methods are used, apart from the determination of the epoxy oxygen content of the epoxy metal soaps. As a result of the insolubility of the epoxy metal soaps in the usual solvents used for the determination of the epoxy oxygen value, this value cannot be determined directly. The metal soap is decomposed, down to the complete decomposition of the soap', at lower temperatures in the presence of ether with 2 N hydrochloric acid. The ethereal solution is subsequently washed with water, dried over anhydrous sodium sulphate and distilled off at a low temperature. The epoxy oxygen value is then determined by the known method on the isolated epoxy fatty acid. Control tests with epoxyand diepoxy-stearic acid show that the test conditions used for the decomposition of the epoxy metal soaps only lead to a negligible reduction of the epoxy oxygen content of the epoxy fatty acid so that this indirect method for the determination of the epoxy oxygen content of the epoxy metal soaps gives a substantially correct value.

The following Table I gives a summary of the physical `constants of the epoxy starting materials.

TABLE I Iodine Epoxydized compound number of Epoxy Saponistarting oxygen, Iodine Acid fication Substance material percent number number number Epoxydized undecylenic acid 152 2. 6-5. 2 2-5 250 Epoxydized methyl ester of undecylenic acid 140 3. 7-5. 6 2. 5 250-260 Epoxydized oleic acid 90 2.7-4.5 1. 5 174-182 Epoxydized methyl ester of ole 90-94 3. 7-4. 6 0. 3-3. 0 0. 5-4 190-191 Epoxydized lnseed oil fatty acid 174 5. 3-6. 7 2-5 175-185 Epoxydized methyl ester of linseed oil fatty acid 160 5. 3-6. 4 1-6 177-189 Epoxydized soyabean oil 150 5.9 10. 4 182 Epoxydized castor oil 52 3. 9 2 3 180 C20-C22 acid mixture 197 3. 8-5. 0 3-5 155-180 Epoxydized methyl ester of C20-C2i acid mixture 190 4. 4-5. 5 3-5 150-170 Epoxydized olive oil 95 4. 2 1 1 184 Epoxydized liuseed oil 190 7.0-7.5 1-2 3.1 186 ucts produced by known processes, preferably from naturally occurring unsaturated fatty acids or their esters. They contain the by-products formed by the opening of the ring of the epoxy group in the epoxydation but the use of pure starting material is also possible in principal. In general, the fatty acid or the fatty acid moiety can contain about 11-22 carbon atoms. Preferred starting materials are epoxydized undecylenic acid, oleic acid, linoleic acid and linolenic acid, either alone or in admixture with one another or with saturated fatty acids, as well as the esters of monoor polybasic alcohols, such as methanol and glycol, obtained therefrom, and the glycerides of these acids.

By epoxydized fatty acids is meant fatty acids containing oxirane rings. There can be one or more than one epoxy group present.

A further advantage of the saponiiication with aqueous alcoholic alkali metal hydroxide solutions is that the crude products obtained after the epoxydation of unsat- -urated fatty acids and of their esters can be converted into the metal soaps via the alkali metal soaps without working up.

The reaction of the alkali metal soaps to the metal soaps takes place by the addition of an aqueous solution of the corresponding metallic salt at room temperature.

The impurities or by-products contained in these technical products iniiuence the physical constants of the metallic soaps produced therefrom but are, however, of no significance for the preferred technical use as polyvinyl chloride stabilizers. The products produced according to the invention consist mainly of the metal soaps of the following acids: l0,llepoxyundecanic acid, 9,10-epoxystea'ric acid, 9,l0,l2,l3diepoxystearic acid, `9,l0,l5,l6 diepoxy-A-lZ, l 3-stearic acid, `9, l0, l2, 13, 15, l6triepoxy stearic acid and the epoxydation products of polyunsaturated C20-C22 fatty acids obtained from fish oils.

The melting range and appearance of the metal soaps produced are to be seen from the following tables.

TABLE IL METAL SOAPS fIIgPOXYDIZED UNDECYLIC Melting range,

C. Appearance 161-166 White powder.

10G-114 Do.

122-135 Redrown, coarse grained powder. 114-118 White powder.

TABLE IIL-METAL SOAPS FROM EPOXYDIZED METHYL TABLE VEL-METAL SOAPS FROM EPOXYDIZED SOY ESTER OF UNDECYLENIC ACID BEAN OIL Melting Melting range, range, Metal Type C. Appearance Motel Type C. Appearance Barium d1 153-157 White powder. 5 Barium di 107-122 Yellowish plastic. Calcium... 102-118 Do. Calcium di 88-i35 Do. Cadmium 11d-118 De: Ca 'um di 155-172 Do. Manganese 85-101 BrQWnlSh-black plastic. Magnesium di 656-102 Whitishyellow, plastic Sodium 160-205 White powder. l mass Zinc S-128 White, Easily 912151210 Zinc di 77-158 Yellowish plastic.

powder. 10

TABLE IX.-METAL SOAPS FROM EPOXYDIZED CASTOR TABLE Iliff-METAL SOi'iPCFIOB'I EPOXYDIZED OLEIC OIL Melting Melting u t 1 range,

range, i c a Type C. Appearance Metal Type C. Appearance 15 l Calcium di 85-100 White, easily plastic Barium di 120-141 Yellowisli powder. powder. Calcium di 97-105 Yellowish, easily plastic Cadmium di 152-155 D0.

powder. l Magnesium di White plastic mass. Cadmium di 84-150 YllOWlSh Smtl'd Sodium mono 91-120 Yellowish powder.

powder. Zinc 105-115 Light yellowish, plastic Magnesium di (J8-115 VOlllmlDGllS Whlte 20 Aluminum mono (l) White powder.

powder. Do (l) White powder, easily Sodium nioiio 1GO-200 White powder: plastic, Manganese di 87-139 Pink, easily sintered Dc tri (1) D0,

powder. Lead dibasic di (2) Yellow, plastic. 00-98 Sintered powder.

(l) White powder. l Above 200. (2) D0: A 25 2 136 sinters up to 200 no clear melting. (3) ellowislli, easily plastic. (1) e owis pow er. q n H02 Light yellow easlly TABLE X. METAL siprlns MiiiirlotR 1UPOXYDIZED C i Cu plastic. lmgovetgoo' t 200 i it Mreiitilgg 70 sin ers, up o no o ear me mg. l y o i 3 45 sinte'is, up to 200 no clear melting. 30 Metal 'lpe C' Appearance Barium di 158-144 Whitisli-yellow, granular TABLE V.METAL SOAIS OF EPOXYDIZED METHYL ESTE R powder.

OF OLEIC ACID Calcium di 95-175 Yelloiiish, granular pow or. Melting Cadmium di 81-89 White powdei.

l'llglgei Magnesium di 80-86 Yellowish, somewhat Metal Typ@ C- Apllamne plastic powder.

1 Manganese di 72-76 Pink, easily sintercd Barium di 85-126 Yellowish, easily plastic Dolmen powder. l l i12-170 Yellewish,easily sintered Calcium... d1 93-1l5 White, easily plastic powder.

l powder. 92-104 Whitish-yellowish, Cadmium. di 90-166 Dol l plastic, Magnesium di 83-80 Yellowish, plastic `mass. 40 Manganese di 8243 vlilrlt: liroiii plastic. S0 llu111- 1.0110 2 lelol'. 'i im L ii u EP YY izn Zinc-U 90'105 Wg'dlsny Plastic TABLE X s'iqibits tiiAcgiD MCiTiIiiinD METHYL Liiiiium meno 200 White powder. Melting range, Metal Type C. Appearance TABLE VL-METAL SOAIS Ol?` EPOXYDIZED LINSEED OIL FATTY ACID Barium di 00-140 White, plastic.

- Calcium di 65-85 Yellewish-White, easily Melting plastic powder. l'allge, Cadmium di 104-180 Yellowish, easily Metal Type C Appearance sintered powder.

Magnesium di 'i2-88 Yellowish-white, plastic Barium di 137-141 Yellowish, easily plastic 50 mags,

POWdl'- Manganese di 811-138 Brown-black, plastic. Calcium di 98-110 Yellowlsll, granular 23S-20o Yciicwish plastic.

DQWBL 155-210 White, granular powder. Cadmium di 81-181 White powder. Magnesium di 105-110 Whito,deasily plastic pow er. l .lllanganos dl 72 83 Wll-ltlslbplnk, easily TABLE XII. METAL SOAPS FROM EPOYDIZED OLD E OIL sinteijed powder. 55 Meltln sodium mono 167-195 Yellowsh, easily plastic mug g pow er. s Zinc di 1033107 agile, piaic powder. Metal TYP C Appeaame Aluminum 1.0110 0 i POW elf: Ceiciuni di tic-e5 white powder.

D d! f2) Lgltlyeuolg; muy cadmium di 12s-147 White, @asiiy sintomo i) Yiivicsnpiasn Owden D0 tii y Lamu di 90.128 Brownish plastic Z111@ d1 77 120 Whl Powder' Do basic di (l) Yellowish powder.

i Above 200, TABLE XML-METAL SOAPS FROM EPOXYDIZED LIN SEED 2 65 sinters, up to 200 no clear melting. OIL 3 40 sinters, up to 200 no clear melting. Melting TABLE VIL-METAL SOAPS FROM EPOXYDIZED METHYL range,

ESTER OF LINSEED OIL FATTY ACID Metal Typ@ C- Appearance Melting Calcium di fis-91 Brownrsh plastic.

range, Cadmium di 95158 Yellowish, easily plastic Mami Type C- Appearance di 62 90 pogder.

Z' o. Barium di 12B-138 Yellowish, sintoiod me powder. Calcium d1 lljgg llllllgvsz Sodium and potassium soaps based upon epoxydized Magnesimn di 89-93 Whted somewhat plastic undecylenc acid and epoxydized oleic acld are white pow er. Sodium mollo 30-173 Whtishyuow, Slightly crystalline Powdels Wlth a melting Poll of 16o-200 C plastic powdl- Ori the other hand, the products obtained, for example, Zinc di 70-110 Yellowish plastic.

from epoxydized linseed fatty acid or epoxydized castor oil are readily adhering powders which are somewhat yellowish in color and have a melting range between 150-200 C. The solubility of the sodium and potassium epoxy soaps in water increases, by equal chain length, with the increasing number of epoxy groups.

The possibility of producing the lithium soaps of epoxy fatty acids is shown in the following, based on the example of the epoxydized methyl ester of oleic acid, from which can be produced lithium epoxy stearate using lithium hydroxide in water-alcohol mixture. It is a white crystalline powder with a melting point of over 200 C.

The partially considerably water-soluble magnesium soaps of the epoxy fatty acids are obtained, by double reaction of their alkali metal soaps with magnesium chloride, as white powders or white to yellowish plastic masses with a melting range of 70-120" C. Their tendency to polymerize with loss of the epoxy oxygen content is considerable, the crystalline magnesium epoxy soaps going over into a plastic state.

The calcium soaps of the epoxy fatty acids are white, crystalline to yellowish readily plastic powders with a melting range of 85-120 C. Their water solubility, with the exception of calcium soap of epoxy linseed fatty acid, is slight, as is also their tendency to polymerize with the splitting off of the epoxy group.

The barium soaps of the epoxydized fatty acids are white crystalline to yellowish, readily plastic, frequently very water soluble substances with a melting range between 100 and 160 C. The tendency of the epoxy group to polymerize is slight.

The cadmium soaps of the epoxydized fatty acids are white crystalline to yellowish readily plastic powders with a melting range between 100 and 180 C. Their water solubility is, in general, slight, as is their tendency to polymerize with the reduction of the epoxy oxygen content.

The zinc soaps of the epoxydized fatty acids are white crystalline to yellowish plastic products with a melting range between 100 and 120 C. Their water solubility is slight and the tendency to polymerize exists only in the case of epoxydized castor oil.

The manganese soaps of the epoxydized fatty acids are pink to red-brown colored crystalline to plastic products with a melting range of between 80 and 130 C. Their tendency to polymerize is light.

The mono, diand tri-aluminum soaps of epoxylized fatty acids can be produced by the reaction of the alkali metal soaps with aluminum sulphate. They are white to pale yellow somewhat sticky powders, whose lower epoxy oxygen content indicates a splitting o of the epoxy group either by polymerization or by the acidic reaction of the aluminum sulphate solution.

Normal and basic lead epoxy soaps can be produced by the double reaction of the alkali metal soaps with lead acetate. They are white-yellowish crystalline to plastic products which have a strong tendency to polymerize with loss of the epoxy oxygen content.

The following examples are given for the purpose of illustrating the present invention:

Example l.-Cadimium soap of epoxydized methyl ester of undecylenic acid 21.4 g. epoxydized methyl ester of undecylenic acid (EpO2 4.5%) are dissolved in 150 ml. 96% ethanol and 4 g. sodium hydroxide in 8O ml. water added thereto at room temperature. One stirs for half an hour at room temperature until the solution has become clear and adds, with stirring, 73 g. of a cadmium nitrate solution (1:5.7 g. cadmium), which contains 78 g. cadmium per kg. One adds three times the volume of water and stirs for a further two hours at room temperature for the purpose of completion of the precipitation. After filtration and washing, the product is dried at 510 C. Yield 24 g.i=94% of the theory, cadmium 21.5%, melting point 11G-188 C., epoxy oxygen of the isolated acid 4.6%.

Example 2.-Dialuminum soap of epoxydized oleic acid 62.4 g. epoxydized oleic acid (Ep02 2.8%) are dissolved in 300 ml. 96% ethanol and 12 g. sodium hydroxide in 240 ml. water added at room temperature. One stirs for half an hour at room temperature until the solution has become clear, adds, with stirring, 33.9 g. aluminum sulphate octadecahydrate in 200 ml. water, adds a further 300 ml. water thereto and subsequently stirs for a further hour. After filtration and washing, the product is dried at 60 C. Yield 70 g., aluminum 4.84%, melting range 70200 C., epoxy oxygen of the isolated acid 0.53%.

Example 3,-Dibasic lead soap from epoxydized oleic acid 31.2 g. epoxydized oleic acid (EpO2 2.92%) are dissolved in 300 ml. 96% ethanol and 12 g. sodium hydroxide in 240i ml. water added thereto at room temperature. One stirs for half an hour at room temperature until the solution has become clear and adds thereto, with stirring, 58 g. lead acetate trihydrate in 300 ml. water, adds a further 300- ml. water thereto and subsequently stirs for a further hour. After ltering and washing, the product is dried at 60 C. Yield 47 g. lead 44.9%, melting point 70-102" C., epoxy oxygen of the isolated acid 2.98%.

Example 1 -Manganese soap of epoxydized methyl ester of oleic acid 31.2 g. epoxydized methyl oleate (EpO2 3.3%) are dissolved in 150 ml. 96% ethanol and 4 g. sodium hydroxide in 80 ml. water added thereto, with stirring, at :room temperature. One stirs for half an hour until a clear solution is obtained and adds 10.4 g. manganese acetate trihydrate thereto as an aqueous solution. One adds three times the volume of water and stirs for a further two hours for the purpose of completion of the precipitation. After ltration, the product is dried at 503 C. Yield 32 g.=99% of theory, manganese 7.2%, melting point 82- 15 8 C., epoxy oxygen of the isolated acid 3.6%.

Example 5,-Zinc soap of epoxydized linseed fatty acid 15.6 g. epoxydized linseed fatty acid (EpO2 4.3%) are dissolved in ml. ethanol and 2 g. sodium hydroxide in 40 ml. water added thereto with stirring. One stirs for half an hour at room temperature until the solution has become clear, adds thereto 7.3 g. zinc sulphate as an aqueous solution, dilutes with three times the volume of water, allows to stand for 60 hours and lilters. The product is dried at 50 C. Yield 17 g.\=99% of theory, zinc 10.1%, melting point 103-107" C., epoxy oxygen of the isolated acid 3.2%.

Example 6.-Cadmium soap of epoxydized linseed fatty acid methyl ester 32.4 g. epoxydized linseed acid methyl ester (EpOZ 6.2%) are dissolved in 150 ml. 96% ethanol and 4 g. sodium hydroxide in ml. water added thereto at room temperature with stirring. One stirs for about half an hour until the solution has become clear and then adds thereto 6.73 g. of a cadmium nitrate solution (==5.7 g. cadmium) which contains 78 g. cadmium per kg. After dilution with three times the volume of water, one stirs for a further two hours and filters. The product is dried at 510 C. Yield 37.5 g.r=97.5% of theory, cadmium 15.6%, epoxy oxygen of the isolated acid 5.4%, melting point 170179 C.

Example 7,-Magnesium soap of epoxydized soybean oil 32.2 g. apoxydized soybean oil (epoxy oxygen 5.2%) are dissolved in ml. 96% ethanol and 4 g. sodium hydroxide dissolved in 80 ml. water added with stirring at room temperature. One stirs for about half an hour until the solution has become clear and adds thereto 10.4 g. magnesium chloride dissolved in Water. After dilution to three times the volume with water, one stirs for two hours and filters 01T. The product is dried at 50 C. Yield 27 g., magnesium 3.1%, epoxy oxygen of the isolated acid 5.6% melting point 66-102 C.

Example 8.-Cadmium soap from epoxydized castor oil 200 g. epoxydized castor oil (EpOZ 4.6%) are dissolved in 925 ml. 96% ethanol and 24.8 g. sodium hydroxide in 495 ml. water added thereto, with stirring, at room temperature. One stirs for about `half an hour, then adds 97 g. cadmium nitrate tetrahydrate in about 500 ml. Water thereto, dilutes at the end of the precipitation with about 1.5 liters water, again stirs for two hours, ilters, washes and dries at about 60 C. Yield 223 g., cadmium 13.4%, melting point IS7-165 C., epoxy oxygen ofthe isolated acid 4.05%

Example 9.-Barium soap of epoxydized C20-C22 acid mixture 15 g. epoxydized `C20-C22 acid mixture (EpOg 3.2%) are dissolved in 62 ml. 96% ethanol and 1.74 g. sodium hydroxide in 32 ml. water added thereto, with stirring, at room temperature. One stirs for about half an hour until the solution has become clear and then adds 5.4 g. barium chloride dihydrate as aqueous solution. After dilution with three times the volume of water, one stirs for two hours at room temperature and iilters ott the product. Drying at 50 C., yield 14 g.f=78% of theory, barium 17.0%, melting point 68-144 C., epoxy oxygen of the isolated acid 2.8%.

Example 10.-Calcium soap of epoxydized methyl ester of C20-C22 acid mixture 30 g. epoxydized methyl ester of C20-C22 acid mixture (EpO2 4.7%) are dissolved in 124 ml. 96% ethanol and 3.3 g. sodium hydroxide in v66 ml. Water added thereto, with stirring, at room temperature. One stirs at room temperature for about halt an hour until a clear solution has been formed and then adds 5.2 g. calcium chloride (91%) as an aqueous solution. After dilution with three times the volume of water, one stirs at room temperature for a further two hours, filters o the product, washes and dries at 50 C. Yield 32 g., calcium 5.0%, epoxy oxygen of the isolated acid 4.2%., melting point 65-85 C.

Example 11.-Calcium soap of epoxidized olive oil 29.8 g. epoxydized olive oil (EpOz 4.0%) are dissolved in a mixture of 10() ml. 96% ethanol and 55 ml. butanol and 4 g. sodium hydroxide in 80 ml. water added thereto at room temperature with stirring. One warms to 30 C. and continues stirring for up to half an hour until a clear solution is obtained 6.2 g. calcium chloride (91%) dissolved in 300 ml. water are then added, with stirring. After dilution with three times the volume of Water, one stirs for two hours, filters oft the product, washes and dries at 50 C. Yield 30.5 g., calcium 4.6%, melting point 90-95 C., epoxy oxygen of the isolated acid, 3.6%.

Example 12,-Zinc soap of epoxidized linseed oil 28.6 g. epoxydized linseed oil (EP02 6.5%) dissolved in 150 ml. ethanol and 4 g. sodium hydroxide dissolved in ml. water added thereto with stirring. One stirs for half an hour at room temperature and then adds 14.65 g. zinc sulphate dissolved in 300 ml. Water. The product is filtered off, washed and dried at 50 C. Yield 28 g., zinc 9.8%, melting point 62-90 C., epoxy oxygen of the osolated acid 6.3%.

What is claimed is:

1. Process for the prouction of polyvalent metal soaps of epoxidized fatty acids, which comprises:

(a) contacting epoxidized fatty acid in an aqueous, al-

coholic, alkaline medium with a monovalent metal cation for saponication to form the salt of the epoxidized fatty acid and said cation, said medium being a solvent for the epoxidized fatty acid and said salt, and containing about l0-70% alcohol based on the alcohol and water present therein, and

(b) contacting said salt with an aqueous solution of a water soluble salt of the said polyvalent metal to form said polyvalent metal soap.

2. Process according to claim 1, said medium containing an alkaline material selected from the group consisting of alkali metal oxides, alkali metal hydroxides and alkaline ammonium compounds, said alkaline material rendering the medium alkaline and providing said monovalent cation.

3. Process according to claim 1, said alcohol content being l0-60%.

4. Process according to claim 1, said medium containing alkali hydroxide, said alkali hydroxide rendering the medium alkaline and providing said monovalent cation.

5. Process according to claim 1, said contacting being at room temperature, said aqueous alcoholic medium containing about 50-70% alcohol based on the alcohol and water present therein.

6. Process according to claim 1, said contacting being at about 40-60 C., said aqueous alcoholic medium containing about 20-50% alcohol based on the alcohol and water present therein.

7. Process according to claim 1, wherein the saponitication is carried out in about 0.5-4 hours.

8. Process according to claim 1, said fatty acid containing about 11-22 carbon atoms.

References Cited UNITED STATES PATENTS 2,684,353 7/1954 Greenspan et al 260-348 FOREIGN PATENTS 754,584 8/ 1956 Great Britain. 825,691 12/ 1959 Great Britain.

JOHN D. RANDOLPH, Primary Examiner U.S. Cl. X.R. 260-45, 398, 656

'2222530 UNITED STATES PATENT OFFICE i CERTIFICATE OF CORRECTXGN Patent No. ,it 59 776 Dated Angus t 5 1969 InventOrCS) Szczepzaneki et al,

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected aS shown below:

Coi. H ne 3, between iester" :md "alkalf should 4. Col. 6, l'm'e 8, kietween "aluminum" and "lead" should be a comma,

5E. Cdl. 74, line 7," '110118" should be 110188.

6. Col. lOQlivne' ZAL, after "47 g. should be a comma.

7. CO1. 10, un@ 38 "503" Should be --50--.

8, COT. TT, une. 56, after "obtainew shpuld be a SGNED 'ND SEALED l MAY 5 1978 Attest: L.

EdwaM F letdmf 1"' i WTLLTAM E. scum, m. ttcstling Ofger l Gomissiwr o! Paten 

1. PROCESS FOR PRODUCTION OF POLYVALENT METAL SOAPS OF EPOXIDIZED FATTY ACIDS, WHICH COMPRISES: (A) CONTACTING EPOXIDIZED FATTY ACID IN AN AQUEOUS, ALCOHOLIC, ALKALINE MEDIUM WITH A MONOVALENT METAL CATION FOR SAPONIFICATION TO FORM THE SALT OF THE EPOXIDIZED FATTY ACID AND SAID CATION, SAID MEDIUM BEING A SOLVENT FOR EPOXIDIZED FATTY ACID AND SAID SALT, AND CONTAINING ABOUT 10-70% ALCOHOL BASED ON THE ALCOHOL AND WATER PRESENT THEREIN, AND (B) CONTACTING SAID SALT WITH AN AQUEOUS SOLUTION OF A WATER SOLUBLE SALT OF THE SAID POLYVALENT METAL TO FORM SAID POLYVALENT METAL SOAP. 